AU669873B2 - Method and apparatus for the controlled reduction of organic material - Google Patents
Method and apparatus for the controlled reduction of organic materialInfo
- Publication number
- AU669873B2 AU669873B2 AU33419/93A AU3341993A AU669873B2 AU 669873 B2 AU669873 B2 AU 669873B2 AU 33419/93 A AU33419/93 A AU 33419/93A AU 3341993 A AU3341993 A AU 3341993A AU 669873 B2 AU669873 B2 AU 669873B2
- Authority
- AU
- Australia
- Prior art keywords
- chamber
- microwave
- controlling
- generator
- feeding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000011368 organic material Substances 0.000 title claims abstract description 24
- 230000009467 reduction Effects 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 88
- 230000005855 radiation Effects 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims 2
- 238000011144 upstream manufacturing Methods 0.000 claims 2
- 239000004058 oil shale Substances 0.000 claims 1
- 230000008569 process Effects 0.000 description 21
- 239000002699 waste material Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
- A62D3/178—Microwave radiations, i.e. radiation having a wavelength of about 0.3 cm to 30cm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B19/00—Heating of coke ovens by electrical means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
- C10B7/06—Coke ovens with mechanical conveying means for the raw material inside the oven with endless conveying devices
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
- C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B6/00—Heating by electric, magnetic or electromagnetic fields
- H05B6/64—Heating using microwaves
- H05B6/78—Arrangements for continuous movement of material
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
- A62D2203/10—Apparatus specially adapted for treating harmful chemical agents; Details thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2206/00—Aspects relating to heating by electric, magnetic, or electromagnetic fields covered by group H05B6/00
- H05B2206/04—Heating using microwaves
- H05B2206/045—Microwave disinfection, sterilization, destruction of waste...
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/145—Feedstock the feedstock being materials of biological origin
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electromagnetism (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Emergency Management (AREA)
- Business, Economics & Management (AREA)
- Optics & Photonics (AREA)
- Environmental & Geological Engineering (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Processing Of Solid Wastes (AREA)
- Constitution Of High-Frequency Heating (AREA)
- Medicines Containing Plant Substances (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Treatment Of Sludge (AREA)
Abstract
There is provided a method and apparatus for the controlled non-pyrolytic reduction of organic material comprising subjecting the material to microwave radiation in a reducing atmosphere. An apparatus for carrying out the method comprises a microwave chamber (40) or modules of chambers, at least one microwave generator (32), an antenna (34) connected to each said generator and a reflecting surface (36). Means are provided for feeding (48) the organic material into the chamber (40), removing (18) gaseous products and solid residue (22) from the chamber.
Description
Method And Apparatus For The Controlled Reduction of Organic Material
FIELD OF THE INVENTION
This application relates to a method and apparatus for the reduction of organic materials using microwave radiation.
BACKGROUND OF THE INVENTION
There are numerous instances in diverse areas where it is desirable that organic materials be reduced. Such a requirement may arise in the processing of raw materials, as, for example, in the extraction of oil from oil shales, or in the treatment of waste materials.
The waste treatment category will arise in an endless number of situations. This may be due to the useful life of the product having been completed. For example, huge quantities of worn out tires are in existence. The waste may also arise from normal industrial processes. Refinery sludge and pulp mill effluents are examples. Municipal sewage and garbage are other sources of large quantities of organic waste.
Various considerations dependent on the particular waste type mandate that the waste be treated. In the case of municipal sewage, for example, the waste is a health and environmental hazard and its toxicity must be neutralized. In the case of tires the emphasis is on recycling of the very substantial amounts particularly of oil and carbon black which are the major components of tires.
The treatment of various of these waste types as, for example, by burning, may itself lead to environmental pollution problems.
There is therefore an ongoing need for more efficient treatment and recycling methods for organic materials.
Against this background the present invention is directed toward the use of microwave energy in a method and apparatus which is applicable in a very general sense to a very wide range of organic materials.
PRIOR ART
Applicant is unaware of any prior use of microwave energy in the treatment of organic materials for non-pyrolytic reduction purposes. Canadian Patent No. 1,158,432, issued December 13, 1983, to Tillitt, suggests the use of microwave energy in drying bulk materials such as grains. The patent offers no aid to the reduction problem discussed above.
U.S. Patent 4,123,230, granted October 31, 1978, to Kirkbride, suggests the use of multiple wave sources, but these are used to provide microwaves of different frequencies. There is no suggestion of focusing nor of creating a uniform or preferred distribution pattern.
U.S. Patent 4,184,614, granted April 10, 1979, also to Kirkbride, describes a somewhat different process than that set out in the preceding reference but contains the same material in respect of the microwave energy.
Similarly, a third Kirkbride patent, U.S. Patent 4,234,402, issued November 18, 1980, describes the same microwave generator arrangement.
U.S. Patent 4,376,034, granted March 8, 1983, to Wall, shows use of a pair of microwave generators at-
opposite ends of a reactor. A very inefficient use of reflected waves is the basis of this microwave application.
The prior art has generally not addressed itself to the more efficient use of microwaves, but has simply incorporated into various processes commercially available microwave generation systems.
BRIEF SUMMARY OF THE INVENTION
It has now been determined that a wide variety of organic materials can be treated with microwave energy for controlling toxicity, for recycling purposes and for various processing purposes.
Thus the invention provides a method for the controlled non-pyrolytic reduction of organic materials which method comprises subjecting the materials to microwave radiation in a reducing atmosphere.
In a further embodiment of the invention there is provided a method for the non-pyrolytic breakdown of longer chain molecules in organic materials which method comprises subjecting molecules to microwave radiation in a reducing atmosphere.
In a further embodiment there is provided an apparatus for the controlled non-pyrolytic reduction of organic material by microwave radiation comprising a microwave chamber, means for feeding the organic material into the chamber, at least one microwave generator in the chamber, means for removing gaseous products from the chamber and means for removing solid residues from the chamber.
BRIEF DESCRIPTION OF THE DRAWING
FIGURE 1 illustrates schematically the method according to the invention;
FIGURE 2 illustrates schematically a microwave generator and parabolic wave guide for use in the invention; and
FIGURE 3 illustrates a pattern for application of microwaves in a preferred embodiment of the invention.
While the invention will be described in conjunction with preferred embodiments, it. will be understood that it is not intended to limit the invention to such embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the following description, similar features in the drawings have been given similar reference numerals.
The method and apparatus of the invention can be applied to an almost limitless variety of organic materials. It is believed that the microwave energy results in the severing of weaker molecular bonds in longer chain molecules to reduce those molecules to simpler forms. This is in effect a de-polymerization process. The process is controlled to avoid pyrolysis of the organic material.
A general schematic of the invention is illustrated in the drawing. Materials are fed into a hopper 10 or into a similar means suitable to the particular feed material. The material is then fed via an air lock 12 into a microwave chamber 14. The material is irradiated by- microwave energy from magnetrons 16.
Gaseous products are taken off to a condenser 18 and condensed to liquid products, generally oils and sulfur.
Solid residues exit the chamber 14 through a second air lock 20. These products are than separated, as by screen 22, into various groups. Carbon black will normally comprise a substantial part of these products. Others would include, for example, steel in the case of tire reduction. Optimum process conditions and apparatus configuration will be selected for a given material after an initial analysis of that material. Several types of analyses are preferably carried out with differing objectives. Thus, an initial analysis of shape and structure may be made with a view to.adapting the microwave chamber and the feeder means to that material. For example, the toroidal shape of tires suggests a different feeder and chamber design than, say, a cube of compressed plastic scrap.
A further analysis is then preferably performed on the material to determine its composition. For example, in treating material which might be categorized essentially as PVC, one would also like to know the quantities of extenders and other such components which might be present.
The results of this analysis will provide information as to the products which are likely to be obtained from the breakdown of the material, the quantities of each such product that might be expected and the order in which the products are likely to be obtained.
A further analysis is then carried out, generally by lab testing, to determine the energy requirement for the process. Having determined that requirement per unit of throughput material, and knowing the volume of material required to be processed, the total energy requirement can be calculated.
The result of these analyses can then be used to optimize apparatus design and process conditions for the various stages in the process.
In the flow of material through the process the first area of concern is in the feeding arrangement.
While the process can be carried out on a batch basis, it is much preferred that it be continuous. Accordingly, since the microwave chamber must be sealed, the feeding apparatus must meet this requirement. One such feeding apparatus design which is useful with a variety of feed material is a piston and cylinder arrangement. For solid feeds a feed hopper can be located above and toward one end of a cylindrical feed conduit to deliver feed material to the conduit. A piston may then be utilized to move the material along the conduit toward the microwave chamber. The continuous plug formed in the feed conduit by the feed material will serve to seal the inlet to the microwave chamber.
A second preferred apparatus for bulk materials and relatively low temperature operations is in the form of an endless belt conveyor. The belt material must be permeable to microwaves and must not itself break down under conditions of use.
For higher temperature operations another preferred feed apparatus comprises one or more stainless steel screw conveyors.
For certain material configurations an airlock may be introduced at the entry to the microwave chamber.
Similarly, in some cases an airlock will be necessary at the solids outlet from the microwave chamber.
The next consideration in the flow of material through the process is the shape of the microwave chamber itself.
Several factors will influence the physical characteristics of the microwave chamber into which the feed material is introduced.
The overall shape of the chamber will generally be chosen based on the physical characteristics of the feed material and the type of feed apparatus utilized. For example, where the piston and cylinder feed arrangement is utilized, a cylindrical chamber may be chosen. Where an endless belt conveyor is utilized, a chamber of rectangular cross-section will generally be preferred.
The overall shape is also influenced by the desire to obtain maximum microwave penetration into the material being processed.
Having determined total power requirements and a basic cross section for the chamber, other factors come into play for purposes of optimization.
A number of variables in the process and apparatus can be predetermined for a given application or controlled in the course of. carrying out the method. For a given application the objective is to obtain the most efficient operation in terms of energy applied per unit mass of material processed, always subject to various process constraints to be discussed.
The manner of applying the total energy requirement in a given case is generally established by a balancing of factors. In order to supply sufficient energy to initiate the reaction in a reasonable time and then to obtain the desired products from the material in the desired sequence, one must appropriately control applied energy. Thus, the basic microwave generation may be obtained from multiple small wave generators rather than from a single magnetron. The output from the wave generators may be continuous, pulsed or otherwise varied. The strength of the microwaves generated can be varied by varying the power input to the generators.
A typical chamber of rectangular cross section might include 4 transverse rows of 3 microwave generators each.
In addition to the arrangement and power of the wave generators, the energy applied per unit mass of treated material will be effected by the time of exposure of the material to the microwave; that is, the dwell time of the material. The energy factors must at this point again be taken in context with chamber geometry. Thus, dwell time may be directly affected by the rate of feed of the material being processed, but, as well, the length of the chamber may be varied and the mass under bombardment may be varied by varying the capacity of the microwave chamber.
Furthermore, the focus of the microwaves contributes markedly to efficiency, and parabolic wave guides have been developed to provide a focus for the waves from a given generator. A series of wave guides may be used with a series of wave generators to provide an overlapping series of microwave curtains to allow very good control of the amount of energy applied to the material.
The surface temperature of the material strongly effects microwave absorption by the material, so it is highly preferable that the surface temperature be monitored and that the power input to the microwave generators be adjusted as required to obtain optimum surface temperature. Thus, as the reactions proceed as the material moves through the microwave chamber, less energy input may be required to maintain optimum surface temperature, so that downstream microwave generators may be operated at lower power input.
It is also useful to monitor the internal temperature of the material in the microwave chamber as a means of predicting what products are likely to be coming off the material at any time. The microwave chamber is preferably kept at slightly above atmospheric pressure. The pressure facilitates removal of gaseous products. It has been found that the process works better in a more dense atmosphere. Accordingly, after the process
is started up and run to the point where the first of the material fed into the chamber has been substantially broken down, the process is found to proceed more efficiently. In that regard the process must be carried out in a reducing atmosphere, and the concentration of reducing gases is increased as the material is broken down. It is theorized that the presence of additional reducing gases may tend to aid in further breakdown of the material, particularly at its surface. It may be preferable in some instances to utilize a two part chamber to isolate the wave generators from the reducing atmosphere. A horizontal microwave permeable gas impermeable barrier would be one solution, with the top and bottom parts of the chamber both being resonant. It may be necessary to add a reducing gas with the feed material. The purpose of the reducing gas is to damp out any oxidation which might otherwise occur during start-up with possible catastrophic results. An inert gas such as nitrogen might also be used, but any compatible reducing gas will do. It should be noted that it is not generally necessary that a reducing gas be added, but that the possibility exists in certain instances.
It has been found that some catalysts enhance the efficiency of the process. Thus, the.addition of carbon black to the input material in the case of tires results in the oils coming off the material more quickly and at lower temperatures.
A further external factor will frequently be present which will be of primary concern in terms of the balancing of the internal factors. The physical space available in a plant to accommodate apparatus according to the invention is often limited, so all of the controllable factors must be balanced in the face of that restriction. The importance of this space consideration is highlighted by the fact that some installations may have a substantial
overall length. For example, lengths in the order of 30 to
60 feet will not be unusual.
In that regard a preferred approach is to utilize a series of modules connected end to end. This has several advantages. Among these is the ability to remove and replace a single module to carry out repairs, thereby avoiding downtime. A further advantage is in ease of manufacture and handling of smaller modules. A preferred module is about 6 feet in length overall. Power availability is a further external variable which may be beyond the control of a user, usually because of the particular location of the plant.
The products of the process are obtained in the form of gaseous and solid material. The gaseous materials are recovered utilizing one or more aspirators on the microwave chamber. The solid products are in the form of residues conveyed through a microwave chamber outlet.
The gaseous products are condensed to provide various hydrocarbon liquids. In that regard it may be necessary to provide heat to the exhaust system to prevent. premature condensation.
The solid products comprise carbon black in micron size and various inorganic materials which may have been present in the feed. For example, in addition to the various oils and carbon black obtained from tires, the residues will include steel, silica and the like components.
For example, a typical PVC lab sample yielded 125 gms solid residue from 160 gms of the original PVC. The residue was almost entirely carbon black containing in total less than 3.159 ppm of the following elements and compounds: As; Ba; B; Cd; Cr; Pb; Se; U; N02 + N03; N02; Ag;
Hg; CN(F) ; F.
As a further example, typical tires will yield per tone of tires, 3 to 4 barrels of oil, 575 to 700 lbs.
of carbon black, 85 to 100 lbs. of steel and 70 to 80 lbs. of fibre.
FIGURES 2 and 3 illustrate a preferred apparatus for carrying out one embodiment of the invention. Microwave generators utilized in ..industrial processes have generally been very inefficient in that they have utilized in general the technique of heating a material simply by bombarding it in a manner which leads to a very non-uniform distribution of microwave energy through the material. The result in such cases is that some parts of the material are undertreated and others overtreated.
In such cases, in order to ensure that all material receives a minimum input of microwave energy, a great deal of energy waste occurs. Furthermore, depending on the material being processed, specific patterns of applied microwaves may be much more efficient than others. With the commonly used general bombarding approach, such varying patterns are not available. Serious problems of energy loss have also existed in using various wave guide types to distribute generated microwaves. For example, some wave guides have had elongated and non-linear paths and have resulted in only weak waves reaching the site of a material to be treated.
Further, a view has been firmly held by some manufacturers of microwave units that multiple wave generators are an impractical solution to the distribution problem because of the problem of interference between waves produced by the various generators. The apparatus of FIGURES 2 and 3 addresses these problems.
FIGURE 2 illustrates a microwave generating apparatus 30 according to the invention comprising a magnetron 32, an antenna 34 and a reflecting surface or wave guide 36. The apparatus 30 is illustrated mounted in wall 38 of a microwave chamber 40. The outer extremity 42
of reflecting surface 36 is mounted flush with wall 38. The opening defined by the extremity 42 of reflecting surface 36 is covered by a ceramic plate 44.
The reflecting surface 36 may be designed to achieve a desired pattern of wave application but in the preferred case is substantially parabolic to provide a substantially circular area of wave application. The top 37 of the reflecting surface 36 is preferably flattened. This allows for easy mounting of the unit but also allows the antenna 34 to be positioned at or near the focus of the parabola.
The boundaries of the pattern may be adjusted by appropriate design of the wave guide in combination with a particular placement of antenna 34. The focus of the pattern can subsequently preferably be adjusted by adjusting placement of antenna 34. The antenna 34 is preferably adjustable over about one inch of travel axially of the reflector 36.
Thus, for example, in the most preferred configuration the combination of the antenna 34 and reflecting surface 36 is adjusted to provide a slightly off focus application of microwaves so that the diameter of the area of application of microwaves is greater than the diameter of the extremity 42 of reflecting surface 36. Application of microwaves is fairly uniform over the circular area.
A series of apparatus 30 can then be arranged as illustrated in FIGURE 3 to provide the desired overlapping pattern 46, the area of which is defined by lines 45 through the outer ones 47 of the generators 30 of the array. In this configuration there is produced in effect a microwave cloud which will provide a reasonably uniform distribution of microwave energy to a material 48 in chamber 40. In a preferred configuration the apparatus 30 is provided with a temperature sensor 50 mounted in the
housing 52 of magnetron 32. Sensor 50 is in turn connected by conductors 51 to a controller 54 which will switch off magnetron 32 via conductors 53 when the sensor 50 registers a limiting temperature and will switch magnetron 32 back on after a preset time period.
Thus, where a non-uniform feed material such as motor vehicle tires is being processed, at times there will be no material beneath an apparatus 30 as, for example, when the open center part of a tire is passing underneath the apparatus. In that case waves reflected from the bottom wall 56 of chamber 40 will cause the apparatus 30 to heat up to the point where the sensor 50 will send a signal to controller 54 causing the magnetron to shut down. After a predetermined period which in the tire case would relate to the time required for the open area of the tire to pass the apparatus 30, magnetron 32 will be switched back on.
This has the combined effect of preventing the apparatus 30 from overheating, and of saving energy.
While the process is widely applicable, and thus highly variable in construction, in a typical case, for example, for reduction of motor vehicle tires, a series of 10 modular tunnels may be used in series to provide a rectangular tunnel of about 60 feet in length and with a cross section of about 14 inches by 36 inches. In a preferred embodiment, two such 60' tunnels would be used in a tire reduction plant. A series of 12 overlapping magnetrons may be used in each module as shown in FIGURE 3. Each magnetron may have 1.5 kilowatts of power at a wavelength of 2450 MHz. The typical process will be carried out at a slight positive pressure of about 1/4 to 1/2 inch of water and at maximum temperatures of about 350*C. The sensor 50 will typically switch off the magnetron at a temperature of about 70*C. Typically the reflectors 36 have a diameter of about 7 1/2 inches to 7 3/4 inches at the extremity of the
parabola. The top section 17 is typically about 3 1/8 inches wide and the reflector about 2 1/2 inches deep.
In the preferred tire plant with twin tunnels, operating under the above conditions, a continuous tire feed rate on a conveyor running at 3 feet per minute will give a dwell time of about 20 minutes and a throughput capacity of 1,440 tires per 24 hours for each 60 foot tunnel.
It is notable that this plant would produce no emissions at all. Gaseous products consist of a narrow band of oils about the consistency of No. 2 diesel fuel, along with elemental sulphur which is condensed separately.
The controlled reduction of the invention avoids emissions problems common in other waste reduction processes, including prior microwave based processes.
Claims (80)
1. A method for the controlled non-pyrolytic reduction of organic material comprising subjecting said material to microwave radiation in a reducing atmosphere.
2. A method for the non-pyrolytic breakdown of longer chain molecules in organic materials comprising subjecting said molecules to microwave radiation in a reducing atmosphere.
3. A method for the controlled non-pyrolytic reduction of organic material by sequentially breaking down molecular bonds in longer chain molecules by subjecting said material to microwave radiation in a reducing atmosphere.
4. The method of claim 1 comprising continuously feeding a stream of said material through a microwave chamber.
5. The method of claim 4 wherein said method comprises feeding said material in an airtight manner relative to said microwave chamber.
6. The method of claim 5 wherein said method comprises feeding said materials into said chamber through a cylinder and propelled by a piston.
7. The method of claim 5 including feeding said material into said chamber on an endless belt conveyor.
8. The method of claim 5 including feeding said material into said chamber by means of a screw conveyor.
9. The method of claim 4 comprising in addition controlling the degree of exposure of said stream to microwave radiation.
10. The method of claim 9 comprising controlling said degree of exposure by controlling the dwell time of said stream in said chamber.
11. The method of claim 10 comprising controlling said dwell time by controlling the rate of travel of said stream through said microwave chamber.
12. The method of claim 10 comprising controlling said dwell time by controlling the length of said microwave chamber.
13. The method of claim 9 comprising controlling said degree of exposure by controlling the power of said microwave radiation.
14. The method of claim 13 comprising controlling said degree of exposure by controlling, in addition, the dwell time of said stream in said chamber.
15. The method of claim 9 comprising controlling said degree of exposure by predetermining the shape of said microwave chamber.
16. The method of claim 15 wherein said chamber is a resonant tunnel whereby microwaves reflected from the walls of said tunnel are in synchronization with said microwave radiation.
17. The method of claim 9 comprising controlling said degree of exposure by focusing said microwave radiation on at least one predetermined point in said stream.
18. The method of claim 1 comprising treating said material in a microwave chamber in which at least one microwave generating unit is disposed.
19. The method of claim 18 in which at least two said generating units are disposed.
20. The method of claim 19 comprising controlling the degree of exposure of said material to microwave radiation by selectively varying the microwave energy output of individual ones of said microwave generating units.
21. The method of claim 18 comprising continuously feeding a stream of said material through said chamber and controlling said microwave generating units to generate a higher level of microwave energy toward an inlet end of said chamber and a lower level of microwave energy toward an outlet end of said chamber.
22. The method of claim 4 wherein said material comprises tires.
23. The method of claim 4 wherein said material comprises municipal garbage.
24. The method of claim 4 wherein said material comprises oil shale.
25. The method of claim 4 including adding a reducing gas to said chamber.
26. The method of claim 4 including adding an inert gas to said chamber.
27. The method of claim 26 wherein said inert gas is Nitrogen.
28. The method of claim 4 wherein said chamber is maintained at a pressure above atmospheric.
29. The method of claim 28 wherein said pressure is in the range of 1/4 to 1/2 inch of water.
30. The method of claim 4 including the step of monitoring the surface temperature of said material in said chamber and controlling the degree of microwave exposure responsive to said monitored temperature.
31. The method of claim 4 including the step of adding a catalyst to said chamber.
32. The method of claim 31 wherein said catalyst is added to said material prior to feeding said material into said chamber.
33. The method of claim 31 or 32 wherein said catalyst is carbon black.
34. The method of claim 4 including the step of continuously removing gaseous products from said chamber.
35. The method of claim 34 wherein said gaseous products are removed sequentially from more volatile/lighter to less volatile/heavier gases.
36. The method of claim 35 wherein the temperature of the material in the chamber is controlled to control the. sequential production of gaseous products from said materials.
37. The method of claim 4 wherein said solid residues are continuously removed from said chamber.
38. A method for the controlled non-pyrolytic reduction of organic material comprising: continuously feeding a stream of organic material into a microwave chamber; maintaining a reducing atmosphere in said chamber; subjecting said material to microwave radiation; and continuously withdrawing gaseous and solid products from said chamber.
39. The method of claim 38 including the step of monitoring the surface temperature of said material.
40. The method of claim 38 including subjecting said material to sufficient microwave radiation to break down longer chain molecules in said material.
41. The method of claim 38 including the step of controlling the amount of microwave radiation to which said material is subjected by controlling at least one of:
(i) the power input to the microwave generator, (ii) the number of microwave generators, (iii) the focus of the microwave generators, (iv) the orientation of the microwave generators, and
(v) the shape of the microwave chamber.
42. The method of claim 41 including the step of controlling the amount of microwave energy to which said material is subjected by controlling at least one of:
(i) the speed of said material through said chamber, and
(ii) the length of said chamber.
43. The method of claim 38 wherein said microwave chamber is maintained at a positive pressure of 1/4 to 1/2 inch of water.
44. The method of claim 38 wherein said method is carried out at a maximum temperature of about 350'C.
45. The method of claim 38 wherein said microwave radiation has a wavelength of about 2450 MHz and produces about 1.5 kW of power.
46. An apparatus for the controlled non-pyrolytic reduction of organic material by microwave radiation according to the method of claim 1, said apparatus comprising: a microwave chamber; means for feeding said material into said chamber; at least one microwave generator in said chamber; means for removing gaseous products from said chamber; and means for removing solid residue from said chamber.
47. The apparatus of claim 46 wherein said chamber is cylindrical.
48. The apparatus of claim 47 wherein said means for feeding comprises a piston and cylinder.
49. The apparatus of claim 46 wherein said chamber is a resonant cavity.
50. The apparatus of claim 46 including at least two said generators arranged in said chamber in an upstream and downstream relationship relative to the flow of said material.
51. The apparatus of claim 50 wherein said upstream generator is of greater power output than said downstream generator.
52. The apparatus of claim 46 including at least one parabolic wave guide for focusing the microwave output of said generator.
53. The apparatus of claim 46 wherein said chamber of rectangular cross section.
54. The apparatus of claim 47 wherein said chamber includes 4 transverse rows of 3 microwave generators each.
55. A modular apparatus for the controlled non- pyrolytic reduction of organic material by microwave radiation, according to the method of claim 1, said apparatus comprising in series at least two modules, the outlet of one module joined to the inlet of the next, each of which modules comprises a microwave chamber and at least one microwave generating apparatus in said chamber; said apparatus further comprising means for feeding said material into a first of said modules and means for removing gaseous and solid products from said series.
56. The apparatus of claim 55 wherein each said chamber is rectangular in cross-section.
57. The apparatus of claim 55 wherein each said microwave generating apparatus comprises: at least one microwave generator; an antenna connected to each said generator for transmitting microwave energy from said generator; and a reflecting surface for reflecting microwave energy from each said antenna in a predetermined pattern onto said material to be treated.
58. The apparatus of claim 57 wherein each said chamber is rectangular in cross section.
59. The apparatus of claim 58 wherein each said chamber includes an array of said microwave generating apparatus for generating microwave radiation in a predetermined overall pattern in said chamber.
60. The apparatus of claim 59 wherein said array comprises 3 rows of 4 said generating apparatus in each row.
61. The apparatus of claim 59 wherein each said generating" apparatus in each said array generates a substantially circular area of microwave radiation.
62. The apparatus of claim 61 wherein each said circular area overlaps with each adjacent said area such that said overall pattern is continuous across said array.
63. A microwave generating apparatus for applying microwave energy to a material to be treated, said apparatus comprising: at least one microwave generator; an antenna connected to each said generator for transmitting microwave energy from said generator; and a reflecting surface for reflecting microwave energy from each said antenna in a predetermined pattern onto said material to be treated.
64. The apparatus of claim 63 wherein the position of said antenna relative to said reflector is adjustable.
65. The apparatus of claim 63 wherein said reflecting surface is parabolic, having an open face.
66. The apparatus of claim 65 having a ceramic plate across said open face.
67. The apparatus of claim 63 including an array of said generators.
68. The apparatus of claim 67 wherein each said pattern is circular area.
69. The apparatus of claim 68 wherein an outer edge of each said pattern overlaps with an outer edge of at least one adjacent pattern.
70. The apparatus of claim 68 wherein each said circular pattern is of slightly greater diameter than the diameter across said face of said reflecting surface.
71. The apparatus of claim 67 wherein said array is a 3 by 4 array.
72. The apparatus of claim 68 wherein said patterns overlap to cover the entire area encompassed within lines through the outer ones of said generators in said array.
73. An apparatus for the controlled reduction of organic materials comprising: a microwave tunnel; and an array of microwave generating apparatus for generating focused microwave energy in said tunnel; each said apparatus comprising (i) at least one microwave generator; (ii) an antenna connected to each said generator for transmitting microwave energy from said generator; and (iii) a reflecting surface for reflecting microwave energy from each said antenna in a predetermined pattern onto said material to be treated.
74. The apparatus of claim 73 wherein each said reflecting surface is parabolic and is mounted with an open face of the parabola substantially flush with a wall of said tunnel.
75. The apparatus of claim 74 having a ceramic plate across said open face.
76. The apparatus of claim 75 wherein said tunnel is of rectangular cross-section having a top wall.
77. The apparatus of claim 76 wherein said array is mounted in said top wall.
78. The apparatus of claim 77 wherein each said predetermined pattern is circular.
79. The apparatus of claim 78 wherein an outer edge of each said pattern overlaps with an outer edge of at least one adjacent pattern.
80. The apparatus of claim 79 wherein said tunnel has a bottom surface and wherein said patterns together cover substantially all of said surface with a substantially uniform amount of microwave energy.
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US82813192A | 1992-01-30 | 1992-01-30 | |
PCT/CA1993/000021 WO1993014821A1 (en) | 1992-01-30 | 1993-01-26 | Method and apparatus for the controlled reduction of organic material |
HK98106048A HK1006949A1 (en) | 1992-01-30 | 1998-06-23 | Method and apparatus for the controlled reduction of organic material |
US828131 | 2007-07-25 |
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US10457930B2 (en) | 2010-06-30 | 2019-10-29 | Microwave Chemical Co., Ltd. | Oil-based material-producing method and oil-based material-producing apparatus |
EP2727647B1 (en) * | 2011-06-29 | 2020-01-15 | Microwave Chemical Co., Ltd. | Chemical reaction apparatus, and chemical reaction method |
JP5114616B1 (en) * | 2011-11-11 | 2013-01-09 | マイクロ波化学株式会社 | Chemical reactor |
US11229895B2 (en) | 2011-11-11 | 2022-01-25 | Microwave Chemical Co., Ltd. | Chemical reaction method using chemical reaction apparatus |
JP5109004B1 (en) | 2011-11-11 | 2012-12-26 | マイクロ波化学株式会社 | Chemical reactor |
CZ304205B6 (en) * | 2012-04-19 | 2014-01-02 | Ústav Chemických Procesů Akademie Věd České Republiky | Decontamination process of solid materials |
PL399250A1 (en) * | 2012-05-21 | 2013-11-25 | Zaklad Mechaniczny Marpo Spólka Jawna M. Przygodzki I Wspólnicy | Method and device for the recycling of organic waste, especially waste tires, by means of microwave technology |
JP5899604B2 (en) * | 2014-03-24 | 2016-04-06 | 兼松エンジニアリング株式会社 | Biomass recycling system using microwaves |
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- 1993-01-26 ES ES93902006T patent/ES2103464T3/en not_active Expired - Lifetime
- 1993-01-26 NZ NZ246544A patent/NZ246544A/en unknown
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- 1993-01-26 PL PL93304711A patent/PL171655B1/en unknown
- 1993-01-26 CZ CZ941834A patent/CZ183494A3/en unknown
- 1993-01-26 CH CH3001/93A patent/CH685431A5/en not_active IP Right Cessation
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- 1993-01-26 DE DE69310151T patent/DE69310151T2/en not_active Expired - Lifetime
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- 1993-01-26 WO PCT/CA1993/000021 patent/WO1993014821A1/en not_active IP Right Cessation
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- 1993-01-26 SK SK917-94A patent/SK91794A3/en unknown
- 1993-01-26 CA CA002129135A patent/CA2129135A1/en not_active Abandoned
- 1993-01-26 DK DK93902006.1T patent/DK0626871T3/en active
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1994
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- 1994-07-29 FI FI943558A patent/FI943558A/en unknown
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NO942838D0 (en) | 1994-07-29 |
ES2103464T3 (en) | 1997-09-16 |
FI943558A0 (en) | 1994-07-29 |
AU3341993A (en) | 1993-09-01 |
CZ183494A3 (en) | 1995-02-15 |
NO942838L (en) | 1994-09-21 |
ATE152000T1 (en) | 1997-05-15 |
BR9305889A (en) | 1997-08-19 |
WO1993014821A1 (en) | 1993-08-05 |
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